CN115036539A - Fuel cell power generation system and control method thereof - Google Patents
Fuel cell power generation system and control method thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04126—Humidifying
- H01M8/04149—Humidifying by diffusion, e.g. making use of membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
- H01M8/04164—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal by condensers, gas-liquid separators or filters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04828—Humidity; Water content
- H01M8/04835—Humidity; Water content of fuel cell reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
- H01M8/222—Fuel cells in which the fuel is based on compounds containing nitrogen, e.g. hydrazine, ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a fuel cell power generation system and a control method thereof, wherein the system comprises an ammonia decomposition device, an ammonia removal device, a fuel cell, a first membrane humidifier, a second membrane humidifier, a first gas-water separator and an air compressor, wherein the first membrane humidifier is communicated between the ammonia decomposition device and an anode of the fuel cell, the second membrane humidifier is communicated between the air compressor and a cathode of the fuel cell, and the air compressor sends compressed air to the cathode of the fuel cell; the first outlet of the fuel cell is communicated with the anode of the fuel cell, the second outlet of the fuel cell is communicated with the inlet of the first gas-water separator, the first outlet of the first gas-water separator is communicated with the first membrane humidifier, and the second outlet of the first gas-water separator is communicated with the second membrane humidifier. The invention unidirectionally sends the water obtained from the cathode side of the fuel cell to the first membrane humidifier at the anode side of the fuel cell through the first gas-water separator, thereby not only reducing the volume of the system, but also fundamentally solving the problem that the anode side of the fuel cell is easy to dry up.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fuel cell power generation system and a control method thereof.
Background
A fuel cell is a chemical device that directly converts chemical energy of fuel into electrical energy, and mainly performs an electrochemical reaction between oxygen or other oxidant and fuel, in which fuel and air are respectively fed into an anode and a cathode of the fuel cell, and electricity is generated. The hydrogen fuel is the most ideal fuel in the current fuel cell application, the efficiency is high, the fuel product is water, no ash residue and waste gas exist, and the environment is not polluted. However, the storage difficulty of hydrogen is high, the ammonia is an alternative fuel of hydrogen at present, and the ammonia has high hydrogen content and has the advantages of easy liquefaction, high energy density, no carbon emission, high safety, low fuel cost and the like.
Proton exchange membrane fuel cell PEMFC is the mainstream technology at present, there are two main problems in the application process, one is that the proton in the perfluorosulfonic acid diaphragm in the PEMFC will react with high-concentration ammonia to generate NH4+ ion, which easily causes the irreversible attenuation of PEMFC performance, and needs to couple a series of component devices such as ammonia decomposition, ammonia removal, hydrogen fuel cell, etc., the high-efficiency integration of these component devices involves complicated energy management and system control strategies, and easily causes the ammonia fuel cell system to operate unstably and consume high energy. The other is that the prior art generally only humidifies the cathode of the fuel cell, and when the proton membrane of the fuel cell stack is thick, membrane dry-out easily occurs on the anode side of the fuel cell.
Chinese patent document CN 110277578A discloses an ammonia fuel cell system and an electric device, which includes an ammonia decomposition reaction device, a heating device, a hydrogen fuel cell, a DC/DC converter and an inverter, a battery pack and a heat exchanger connected in sequence, can stably operate for a long time, form cyclic utilization, and have the advantages of high flexibility, low energy consumption and high system utilization rate. The patent technology has solved the first problem, but the second problem is to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problem that the anode side of the fuel cell is easy to dry up when the proton membrane of the conventional fuel cell stack is thick, and therefore, the invention provides a fuel cell power generation system and a control method thereof.
The invention adopts the following technical scheme:
in one aspect, the present invention provides a fuel cell power generation system comprising:
the ammonia decomposition device is used for decomposing ammonia gas into hydrogen and nitrogen;
the ammonia removal device is communicated with the outlet of the ammonia decomposition device and is used for removing undecomposed ammonia gas;
a fuel cell, which is communicated with the ammonia removal device and takes hydrogen as fuel to be oxidized to generate electric energy;
a converter connected to the fuel cell and boosting a voltage of the fuel cell;
a battery pack for storing electric energy generated by the fuel cell;
the system also comprises a first membrane humidifier, a second membrane humidifier, a first gas-water separator and an air compressor; the first membrane humidifier is communicated between the ammonia decomposition device and the anode of the fuel cell, the second membrane humidifier is communicated between the air compressor and the cathode of the fuel cell, and the air compressor is used for sending compressed air to the cathode of the fuel cell; the first outlet of the fuel cell is communicated with the anode of the fuel cell, the second outlet of the fuel cell is communicated with the inlet of the first gas-water separator, the first outlet of the first gas-water separator is communicated with the first membrane humidifier, and the second outlet of the first gas-water separator is communicated with the second membrane humidifier.
Furthermore, the system also comprises a membrane separation device and a pressure swing adsorption separation device, wherein the inlet of the pressure swing adsorption separation device is communicated with the outlet of the membrane separation device, the outlet of the ammonia removal device is communicated with the inlet of the membrane separation device, and the outlet of the pressure swing adsorption separation device is communicated with the anode of the fuel cell through the first membrane humidifier.
Further, the system also comprises a hydrogen booster pump which is connected between the outlet of the ammonia removal device and the inlet of the membrane separation device.
And furthermore, the system also comprises an ejector, wherein an inlet of the ejector is communicated with the first outlet of the fuel cell, the first outlet of the ejector is respectively communicated with an outlet of the pressure swing adsorption separation device and an inlet of the ammonia decomposition device, and a second outlet of the ejector is communicated with the anode of the fuel cell.
Preferably, the heating device comprises an electric heater and a tail gas combustion device, the ammonia decomposition device is internally separated by a first decomposition space and a second decomposition space which can conduct heat, the tail gas combustion device is installed in the first decomposition space, and the electric heater is installed in the second decomposition space; the first decomposition space is communicated with a first inlet of the ammonia decomposition device and a first outlet of the ejector respectively, the second decomposition space is communicated with a second inlet of the ammonia decomposition device, ammonia gas enters the second decomposition space, and the first decomposition space and the second decomposition space are communicated with an outlet of the ammonia decomposition device.
Preferably, the second decomposition space is filled with two catalysts along the flow direction of the ammonia gas, the proportion of the first catalyst arranged near the upstream side of the ammonia gas is gradually increased, and the proportion of the second catalyst arranged near the downstream side of the ammonia gas is gradually increased.
Further preferably, the first catalyst adopts a Ru-based catalyst, the second catalyst adopts a Ni-based catalyst, the catalyst ranges are distributed and filled in a gradient mode, and the particle size of the catalyst is 0.5mm-3 mm.
In another aspect, the present invention also provides a fuel cell power generation system including:
the ammonia decomposition device is used for decomposing ammonia gas into hydrogen and nitrogen;
the ammonia removal device is communicated with the outlet of the ammonia decomposition device and is used for removing undecomposed ammonia gas;
a fuel cell, which is communicated with the ammonia removal device and takes hydrogen as fuel to be oxidized to generate electric energy;
a converter connected to the fuel cell and boosting a voltage of the fuel cell;
a battery pack for storing electric energy generated by the hydrogen fuel cell;
the system also comprises a booster pump, a hydrogen circulating pump, a third membrane humidifier, a second gas-water separator and an air compressor, wherein the inlet of the booster pump is connected with the outlet of the ammonia removal device, the outlet of the booster pump is communicated with the anode of the fuel cell, and the air compressor is used for sending compressed air into the booster pump;
the third membrane humidifier is communicated between the booster pump and the cathode of the fuel cell; the first outlet of the fuel cell is communicated with the inlet of the hydrogen circulating pump, the first outlet of the hydrogen circulating pump is communicated with the inlet of the ammonia decomposition device, the second outlet of the hydrogen circulating pump is communicated with the anode of the fuel cell, the second outlet of the fuel cell is communicated with the inlet of the second gas-water separator, and the outlet of the second gas-water separator is communicated with the third membrane humidifier.
Further, the system still includes hydrogen booster pump and membrane separation device, membrane separation device 7 the first export with the first export intercommunication of hydrogen circulating pump, membrane separation device's second export with the booster pump intercommunication, the hydrogen booster pump import with ammonia stripping means exit linkage, the hydrogen booster pump export with membrane separation device import intercommunication.
The invention also provides a control method of the fuel cell power generation system, which comprises the following steps:
s101: starting the heating device, and when the interior of the ammonia decomposition device reaches a preset temperature, sending ammonia gas into the ammonia decomposition device to decompose the ammonia gas into hydrogen and nitrogen;
s102: the decomposed hydrogen and nitrogen gas enters an ammonia removal device to remove undecomposed ammonia gas;
s103: the deaminated hydrogen and nitrogen enter a hydrogen booster pump, and the hydrogen and nitrogen are boosted to a preset pressure;
s104: the pressurized hydrogen and nitrogen enter a membrane separation device to carry out primary separation on hydrogen, and the hydrogen and nitrogen after membrane separation enter a pressure swing adsorption separation device to carry out secondary separation on the hydrogen;
s105: the separated hydrogen and nitrogen enter the anode of the fuel cell after the humidity of the hydrogen and nitrogen is adjusted by the first membrane humidifier, and the compressed air enters the cathode of the fuel cell after the humidity of the compressed air is adjusted by the second membrane humidifier; gas generated by the anode of the fuel cell flows back to the ammonia decomposition device, the pressure swing adsorption separation device and the anode of the fuel cell under the action of the ejector, the gas generated by the cathode of the fuel cell is separated into air and water through the first gas-water separator, and the first gas-water separator respectively sends the separated water to the first membrane humidifier and the second membrane humidifier;
s106: the conversion device boosts the fuel cell voltage and stores the generated electric energy to the battery pack.
The invention also provides a control method of the fuel cell power generation system, which comprises the following steps:
s201: starting a heating device, and when the interior of the ammonia decomposition device reaches a preset temperature, sending ammonia gas into the ammonia decomposition device to decompose the ammonia gas into hydrogen and nitrogen;
s202: the decomposed hydrogen and nitrogen gas enters an ammonia removal device to remove undecomposed ammonia gas;
s203: the deaminated hydrogen and nitrogen enter a hydrogen booster pump, and the hydrogen and nitrogen are boosted to a preset pressure;
s204: the pressurized hydrogen and nitrogen enter a membrane separation device to carry out membrane separation on the hydrogen, and the hydrogen and nitrogen after membrane separation are pressurized by a booster pump and then are sent to the anode of the fuel cell; the compressed air is pressurized by a booster pump and then sent into a third membrane humidifier, and the compressed air enters the cathode of the fuel cell after the humidity of the compressed air is adjusted by the third membrane humidifier; gas generated by the anode of the fuel cell flows back to the ammonia decomposition device, the membrane separation device and the anode of the fuel cell under the action of a hydrogen circulating pump, the gas generated by the cathode of the fuel cell is separated into air and water through a second gas-water separator, and the second gas-water separator sends the separated water to a third membrane humidifier;
s205: the conversion means boosts the fuel cell voltage and stores the generated electric energy to the battery pack.
The technical scheme of the invention has the following advantages:
A. the fuel cell power generation system provided by the invention is characterized in that the anode and the cathode of the hydrogen fuel cell are respectively provided with the membrane humidifier, and the membrane humidifier can humidify the anode and the cathode of the fuel cell respectively, so that the problem that the anode side of the fuel cell is easy to dry when the proton membrane of the fuel cell stack is thick due to only humidifying the cathode of the fuel cell in the prior art is solved.
B. The first membrane humidifier, the second membrane humidifier and the third membrane humidifier all adopt Nafion membranes, water obtained by the first gas-water separator on the cathode side of the fuel cell is sent to one side of the first membrane humidifier on the anode side of the fuel cell in a one-way mode, and hydrogen cannot permeate out due to the fact that the Nafion membranes are arranged on one side and on the other side under the condition that water is arranged on one side and hydrogen is arranged on the other side.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings which are needed to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained from the drawings without inventive labor to those skilled in the art.
Fig. 1 is a diagram showing a fuel cell power generation system according to a first embodiment of the present invention;
fig. 2 is a diagram showing a fuel cell power generation system according to a second embodiment of the present invention;
FIG. 3 is a flowchart of a control method for a fuel cell power generation system according to an embodiment;
fig. 4 is a flowchart of a method for controlling a fuel cell power generation system according to a second embodiment.
The designations in the drawings are as follows:
1-an ammonia decomposition unit; 2-a heating device; 3-a first control valve; 4-Ammonia removal device
5-a second control valve; 6-hydrogen booster pump; 7-a membrane separation device; 8-third control valve
9-pressure swing adsorption separation device; 10-a fourth control valve; 11-a first membrane humidifier;
12-an ejector; 13-a fuel cell; 14-a first gas-water separator; 15-second membrane humidifier
16-an air compressor; 17-a DC/DC converter; 18-a battery pack; 19-capacitance; 20-DC load
21-an alternating current load; 22-a booster pump; 23-a hydrogen circulation pump; 24-third Membrane humidifier
25-second gas-water separator.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; the connection can be mechanical connection or electrical connection; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
As shown in fig. 1, the present invention provides a fuel cell power generation system including: the ammonia decomposition device 1, the heating device 2, the ammonia removal device 4, the fuel cell 13, the conversion device, the battery pack 18, the first membrane humidifier 11, the second membrane humidifier 15, the first gas-water separator 14, the air compressor 16, and the like.
The heating device 2 is arranged in the ammonia decomposition device 1 and used for heating gas and a catalyst, and the ammonia decomposition device 1 is used for decomposing ammonia gas into hydrogen and nitrogen;
the inlet of the ammonia removal device 4 is communicated with the outlet of the ammonia decomposition device 1 and is used for removing undecomposed ammonia gas; the fuel cell 13 is communicated with the ammonia removal device 4, and hydrogen is used as fuel to be oxidized to generate electric energy; the converter is connected to the fuel cell 13, and boosts the voltage of the fuel cell 13; the battery pack 18 is used for storing electric energy generated by the fuel cell 13; the first membrane humidifier 11 is communicated between the ammonia decomposition device 1 and the anode of the fuel cell 13; the second membrane humidifier 15 is communicated between an air compressor 16 and the cathode of the fuel cell 13, the air compressor 16 is used for sending compressed air to the cathode of the fuel cell 13; the first outlet of the fuel cell 13 communicates with the anode of the fuel cell 13, the second outlet of the fuel cell 13 communicates with the inlet of the first gas-water separator 14, the first outlet of the first gas-water separator 14 communicates with the first membrane humidifier 11, and the second outlet of the first gas-water separator 14 communicates with the second membrane humidifier 15.
According to the fuel cell power generation system, the membrane humidifiers are respectively arranged at the anode and the cathode of the hydrogen fuel cell, and the Nafion membrane is adopted, so that the problem that only the cathode of the fuel cell is humidified in the prior art is solved, and when the proton membrane of the fuel cell stack is thick, the problem that the membrane is dry easily occurs on the anode side of the fuel cell. The invention humidifies the anode of the hydrogen fuel cell, one is that the water obtained by the first gas-water separator 14 on the cathode side of the fuel cell 13 is sent to one side of the first membrane humidifier 11 on the anode side of the fuel cell 13 in a one-way mode, because the hydrogen cannot permeate out under the condition that one side of the Nafion membrane is water and the other side of the Nafion membrane is hydrogen; the other method adopts the anode exhaust gas of the fuel cell 13 for humidification, and can also ensure the purity of the anode hydrogen, but the humidification of the anode exhaust gas of the fuel cell 13 is insufficient. The present invention adopts the former humidification mode, and the combined use of the two modes is the best mode proposed in the present embodiment, which not only can reduce the system volume, but also fundamentally solves the problem that the anode side of the fuel cell 13 is easy to dry up. Humidification of the fuel cell 13 anode with humid air results in hydrogen breakthrough, which further reduces the hydrogen concentration to inoperability due to the hydrogen and nitrogen used in the system. In the operation process, the humidification quantity is adjusted and controlled according to the feedback of working parameters in the galvanic pile, the humidity control range is 10-90% RH, and the temperature control range is 10-45 ℃.
In this embodiment, the system further includes a membrane separation device 7 and a pressure swing adsorption separation device 9, an outlet of the membrane separation device 7 is connected to an inlet of the pressure swing adsorption separation device 9, an inlet of the membrane separation device 7 is connected to an outlet of the ammonia removal device 4, and an outlet of the pressure swing adsorption separation device 9 is communicated with an inlet of the first membrane humidifier 11. The volume ratio of hydrogen to nitrogen in the deaminated hydrogen and nitrogen is 3:1, the deaminated hydrogen and nitrogen is separated and purified by adopting the coupling of a membrane separation device 7 and a pressure swing adsorption separation device 9, the gas firstly enters the membrane separation device 7 and then enters the pressure swing adsorption separation device 9, and the circulating gas separated by the pressure swing adsorption is returned to the membrane separation device 7 for recycling. The order of the membrane separation device 7 and the pressure swing adsorption separation device 9 cannot be changed, because the upper limit of the concentration of the hydrogen separated by the membrane separation device 7 is 95 percent, although the cost is low and the whole working condition is good, the hydrogen with the concentration is not satisfactory for the fuel cell 13 system; the upper limit of the concentration of the hydrogen separated by the pressure swing adsorption separation device 9 can reach 99.97-99.999 percent, the purity can reach high, but the cost is high, the pressure swing adsorption separation device can not adapt to the change of working conditions, and the yield is very low under low working conditions. The inventor researches and discovers that after membrane separation and pressure swing adsorption separation are combined, the membrane separation and the pressure swing adsorption separation can simultaneously deal with low working conditions and high working conditions, and extremely high yield can be obtained, so that the sequence of the membrane separation device 7 and the pressure swing adsorption separation device 9 cannot be changed, and the design can be simultaneously adapted to various hydrogen concentrations, because the yield is ensured in a purification mode, and the performance of the fuel cell 13 is ensured in humidification and equivalence ratio.
In specific implementation, the membrane separation device 7 can adopt polysulfone, 2, 6-dimethylphenylene oxide (PPO), aromatic polyamide, polyimide, modified polycarbonate, cellulose acetate and other polymer membranes, and performs hydrogen permeation separation on hydrogen and nitrogen under the conditions that the use temperature is 20-140 ℃ and the pressure difference between two sides is 0.1-3.2 MPa; the upper limit of the hydrogen concentration after membrane separation can reach 95%, and the upper limit of the yield can reach 95%. The purity of the hydrogen after the adsorption and separation of the pressure swing adsorption separation device 9 reaches 99.97-99.999 percent, and the desorbed gas is pumped back to the membrane separation part for circulation.
In addition, the conventional PEMFC pile system cannot stably operate under a hydrogen-nitrogen mixture, and the stable operation is possible by adopting the membrane separation device 7 and the pressure swing adsorption separation device 9 in a coupling way.
In this embodiment, a hydrogen booster pump 6 is further provided, and the hydrogen booster pump 6 is connected between the ammonia removal device 4 and the membrane separation device 7, and is used for boosting the hydrogen and nitrogen. The ammonia decomposition reaction is a reaction in which the equilibrium moves in the reverse direction as the pressure increases; meanwhile, for the fuel cell 13, if the pressure of the hydrogen and nitrogen is low, the required pressure of the stack of the fuel cell 13 cannot reach 0.15-0.2MPa (1.5-2.0bar), so the hydrogen and nitrogen after deamination is pressurized by the hydrogen booster pump 6 to meet the requirement of the fuel cell 13.
In this embodiment, an ejector 12 is further provided in the system, an inlet of the ejector 12 is communicated with a first outlet of the fuel cell 13, the first outlet of the ejector 12 is respectively communicated with an outlet of the pressure swing adsorption separation device 9 and an inlet of the ammonia decomposition device 1, and a second outlet of the ejector 12 is communicated with an anode of the fuel cell 13. On one hand, the ejector 12 can lead the gas correspondingly generated by the anode of the fuel cell 13 to flow back to the anode of the fuel cell 13, can lead the hydrogen to be circularly oxidized and can also play a certain role in humidifying the hydrogen; on the other hand, the gas generated by the anode of the fuel cell 13 correspondingly may be returned to the pressure swing adsorption device, and may enter the anode of the fuel cell 13 after passing through the first membrane humidifier 11; on the other hand, the gas generated by the anode of the fuel cell 13 may be returned to the ammonia decomposition device 1, and the temperature inside the ammonia decomposition device 1 may be maintained by the heat of the exhaust gas, and the hydrogen gas may be recycled.
In this embodiment, the heating device 2 includes an electric heater and a tail gas combustion device, the ammonia decomposition device 1 includes two decomposition spaces which are isolated and can conduct heat conduction, the first decomposition space is communicated with the first outlet of the ejector 12 through the first inlet of the ammonia decomposition device 1, and the tail gas combustion device is installed in the first decomposition space; ammonia gas can enter the second decomposition space through a second inlet of the ammonia decomposition device 1, and the electric heater is arranged in the second decomposition space; the first and second decomposition spaces are both in communication with the outlet of the ammonia decomposition device 1. The second decomposing space is filled with two catalysts along the flow direction of the ammonia gas, the proportion of the first catalyst arranged near the upstream side of the ammonia gas is gradually increased, and the proportion of the second catalyst arranged near the downstream side of the ammonia gas is gradually increased.
Wherein, the tail gas burner mainly is the heat supply function, and electric heater is the temperature control function. The combustion device is a microchannel reactor for carrying out catalytic oxidation heat release on tail gas, wherein the hydrogen concentration of the tail gas is 20-70%, and the electric heater plays a role in controlling temperature and supplementing heat, and the heat exchange is enhanced by utilizing the modes of surrounding fin contact, embedding the other side of the fin into an inner tube catalyst bed layer and the like; the electric heater can additionally give thermal power to the downstream side close to the gas according to a temperature control instruction, so that the performance of catalysts such as Ni-based catalysts under the pressure of 0.4Mpa is ensured; the microchannel reactor has the function of heat exchange between low-temperature gas and high-temperature gas entering the device, realizes the inlet temperature of the low-temperature gas of-5-45 ℃, the temperature of the low-temperature gas reaching a catalyst bed layer of 450-600 ℃, and the temperature of the high-temperature gas leaving the ammonia decomposition reactor after decomposition is lower than 150 ℃.
Among them, the first catalyst is preferably a Ru-based catalyst, and the second catalyst is preferably a Ni-based catalyst. Along the flowing direction of ammonia gas, Ru-based and Ni-based catalysts are filled from top to bottom, the catalyst is filled in a gradient manner, the particle size of the catalyst is 0.5-3 mm, and the shape of the catalyst is not limited to spherical porous particles and strip-shaped porous particles; wherein the working temperature of the upstream part is 480 ℃, and the downstream part can be operated at 500-650 ℃ according to instructions; the tail gas combustion device adopts hydrogen catalytic oxidation, and the working concentration range is 20-70%.
The Ru-based multiphase catalyst arranged closer to the gas upstream side has higher proportion, the Ni-based catalyst arranged closer to the gas downstream side has higher proportion, and the proportion of the components of the two catalysts is distributed in space in a plurality of component distribution ratio modes including but not limited to free mixing, linear distribution and the like; the decomposition temperature of the bed layer ammonia reaches 99.8 percent of decomposition rate at 480 ℃, and the method of improving the decomposition rate by temperature gradient at 0.4Mpa pressure and 10000mL (gcat. h) space velocity can reach 99.8 percent of decomposition rate; the above decomposition rate refers to the conversion per pass of hydrogen production by ammonia decomposition. Because the ammonia decomposition reaction is a reaction which moves along with the increase of pressure and balance in a reverse direction, the pressurization tests on the catalyst are very large, the idea of industrial treatment is to increase the temperature, but the Ru-based catalyst cannot be carried out at an overhigh temperature for some reasons, otherwise, the carrier can be dissociated and pulverized on structural mechanics, and the system can absorb heat violently at the air inlet end in dynamics, so that the temperature of a heat exchange pinch point cannot be effectively controlled, the heat exchange efficiency is reduced violently, and the reason is that the arrangement of the gradient distribution of the upper layer and the lower layer of the Ru-based catalyst is adopted, and the heat dissipation capacity can be uniformly distributed on the whole tube pass.
Further explaining the action of the catalyst, the Ru-based catalyst has low activation temperature and high conversion rate, but the carrier is not heat-resistant, if the catalyst needs to be heated when running at high pressure, the heat absorption of the front section of the tube pass can be caused quickly, so that the heat exchange efficiency is greatly reduced, and the temperature of the rear end of the tube pass is high, so that the catalyst is pulverized. The activation temperature of the Ni-based catalyst is high, higher temperature is needed, if only the Ni-based catalyst is used, the temperature of the front section of a tube pass is low, the heat exchange efficiency is greatly reduced, the volume of a system is greatly increased, and the design which can be realized but is difficult to be practically applied is realized, so that the Ni-based catalyst and the Ni-based catalyst are necessary to be fused for use.
Among the above-mentioned fuel cell power generation system, ammonia decomposition device 1 is equipped with first import, second import and export, and ammonia decomposition device 1's first import and ejector 12 intercommunication, ammonia decomposition device 1's second import pass through the flowmeter and store up ammonia tank intercommunication, and ammonia decomposition device 1's export and ammonia removal device 4 intercommunication. In specific implementation, a first decomposition space and a second decomposition space are separated from each other by a heat-conducting metal structure in the ammonia decomposition device 1, and as an implementation mode, the heat-conducting metal structure is a heat-conducting metal plate, and the first decomposition space and the second decomposition space are separated from each other in the left-right direction; in another embodiment, the heat-conducting metal structure is a tubular structure, tail gas enters a first decomposition space in the tubular structure, and ammonia gas enters a second decomposition space outside the tubular structure; compare in heat conduction metal sheet, adopt tubular structure can let the heat of tail gas burning be the heating of second decomposition space better, improve tail gas heat utilization efficiency.
According to the fuel cell power generation system, the first membrane humidifier 11 and the ejector 12 are combined to control the humidity of hydrogen entering the anode of the fuel cell 13, and the second membrane humidifier 15 and the air compressor 16 are combined to control the humidity of air entering the cathode of the fuel cell 13, so that the first membrane humidifier 11, the second membrane humidifier 15, the ejector 12 and the air compressor 16 are combined to be used, and the humidity of the hydrogen entering the fuel cell 13 is controlled. The ejector 12 is adopted to enable tail gas generated by the anode of the fuel cell 13 to flow back to the ammonia decomposition device 1, so that heat of the tail gas is effectively utilized, meanwhile, the tail gas combustion device is adopted to provide heat, and the electric heater is used for controlling the temperature, so that the ejector 12, the tail gas combustion device 2 and the electric heater are used in a combined mode, and the temperature of hydrogen of the fuel cell 13 is controlled. The hydrogen pressurized by the hydrogen booster pump 6 enters the anode of the fuel cell 13 from the first inlet of the fuel cell 13, the ejector 12 returns the tail gas of the fuel cell 13 to the anode of the fuel cell 13 through the first inlet of the fuel cell 13, and the air is compressed by the air compressor 16 and then enters the cathode of the fuel cell 13 from the second inlet of the fuel cell 13, so that the dynamic pressure balance between the air and the tail gas outlet of the anode of the fuel cell 13 is realized. And then, temperature, humidity and pressure control is realized on the hydrogen at the first inlet of the fuel cell 13, the equivalent ratio, humidity and pressure of the gas leaving from the first outlet of the fuel cell 13 are controlled on the anode exhaust coupling of the first inlet of the fuel cell 13, the pressure, humidity and temperature control is performed on the air at the second inlet of the fuel cell 13, and the dynamic pressure balance between the air and the gas at the first outlet of the fuel cell 13 is realized.
The tail gas pressure control of the first outlet of the fuel cell 13 comprises a hydrogen booster pump 6 which is based on the Pasco principle and utilizes a compressed air source, and compressed air entering through a second inlet of the coupled fuel cell 13 is used for boosting the gas of the first outlet of the fuel cell 13; the pressure control range is 0.1MPa-0.4 MPa; the absolute value of the gas pressurization of the first outlet of the fuel cell 13 is 1-4 times of the pressure drop value of the compressed air, the pressure cooperative control is realized through the controller, and the value difference between the first outlet pressure of the fuel cell 13 and the second outlet pressure of the fuel cell 13 is controlled to be 0-0.08 MPa.
Among these, the hydrogen-nitrogen mixture obtained by decomposing ammonia to produce hydrogen results in unacceptable fuel cell 13 systems generally used for pure hydrogen, because ejector 12 is directly stopped and the circulating pump also causes nitrogen accumulation, which is a key problem in terms of equivalence ratio and humidity. The gas equivalence ratio control of the first outlet of the fuel cell 13 of the embodiment adjusts the gas equivalence ratio entering the fuel cell 13 system according to the set purity parameters of the membrane separation device 7 and the pressure swing adsorption separation device 9, the humidification part strategy and the electric pile operation condition; the equivalence ratio is calculated based on the hydrogen consumed by the fuel cell 13 stack, and is controlled in the range of 1.2-1.6. The pressure at the front end of the ejector 12 is controlled to be 1.35-1.5 MPa.
The method comprises the following steps that (1) the tail gas of a fuel cell 13 stack is controlled, an ejector 12 is used for pumping anode tail gas to a first inlet of the fuel cell 13, the rotating speed of the ejector 12 is controlled to realize equivalence ratio and humidity control, and gas backpressure is adjusted; the gas water vapour from the cathode of the fuel cell 13 is reverse-osmotically fed back to the second inlet of the fuel cell 13 by means of the first and second membrane humidifiers 11, 15.
In this embodiment, the fuel cell 13 employs a proton exchange membrane, i.e., a PEMFC stack using a perfluorosulfonic acid membrane and a modified membrane thereof as an electrolyte, or an HT-PEMFC stack using a phosphoric acid-PBI-doped or PBI/SiO2 composite membrane as an electrolyte, and has a working temperature of 50 to 90 ℃, a suitable gas of 75 to 99.999% pure hydrogen, an ammonia gas concentration of less than 0.1ppm, a use humidity range of 10 to 95% RH, and a use air pressure range of 0.1 to 0.4 MPa; the HT-PEMFC pile is suitable for hydrogen with 75-99.999% purity of gas, ammonia gas with the concentration less than 100ppm, the use humidity range of 60-99.9% RH and the use air pressure range of 0.1-0.3 MPa.
In the embodiment, the air compressor 16 outputs 0.1-0.4MPa of compressed air according to the controller, the flow rate is matched with the power of the fuel cell 13 stack, and the adjustment range is 1.5-2.2 according to the equivalence ratio of air entering the fuel cell 13; the air compressor 16 air intake is fitted with an air filter to filter ambient particulates.
In the embodiment, the ammonia removal device comprises a plurality of groups of ammonia removal devices, the ammonia removal devices absorb ammonia in the hydrogen-nitrogen mixed gas from the ammonia decomposition device by a physical absorption method, the working pressure range of the absorbent is 0.1-0.4Mpa, the working temperature is 30-110 ℃, the ammonia content of the gas absorbed by the device is less than 0.1ppm, and the temperature is less than 45 ℃.
In the present embodiment, the conversion device employs a DC/DC converter 17 to deliver the electricity generated by the fuel cell 13 to the output terminal in accordance with the CC, CV or CP mode, and is connected to the battery pack 18 and an external DC load 20 or ac load 21. The capacitor 19 and the battery pack 18, and a self-contained BMS system can respond to the change of external requirements by the discharge multiplying power of 0.1-10C, and can realize the direct current bus load adaptation with the voltage of the DC/DC output end.
The hydrogen fuel cell power generation system of the embodiment has the advantages of high hydrogen energy storage density, high energy conversion efficiency and low power generation cost, has a great application prospect in the scenes of mines, construction sites, islands, oil field exploration and the like far away from a power grid or data centers with large power loads, offshore platforms and the like as a power generation unit, and has a greater application advantage in some biomedical parks and hospital scenes compared with 2.5-2.8 yuan/kWh of a diesel power generation unit, wherein the use cost of the ammonia hydrogen fuel cell 13 is 1.6 yuan/kWh, the noise of the system is small, and no pollutant is discharged.
The working process of the fuel cell power generation system is as follows:
ammonia gas enters an ammonia decomposition device 1 after passing through a flowmeter, and a heating device 2 consisting of an electric heater and a tail gas combustion device supplies heat to heat the ammonia gas and a catalyst, so that the ammonia gas is decomposed into hydrogen and nitrogen; specifically, the two modes supply heat together when the catalyst is started, the electric heating system only plays a role in controlling the temperature after the catalyst is started, so that ammonia is decomposed into hydrogen and nitrogen in a catalyst bed, the decomposition rate reaches over 99.8%, the decomposition pressure can be increased to 0.5MPa according to the rear end requirement, and the catalyst is realized by cooperating with a rear-end electric heater and a bed with high Ni-based catalyst content. The decomposed hydrogen and nitrogen gas passes through a first control valve 3 and then enters an ammonia removal device 4, and undecomposed ammonia gas is removed to obtain the hydrogen and nitrogen gas with the ammonia content of less than 0.1 ppm; the deaminated hydrogen and nitrogen gas enters a hydrogen booster pump 6 after passing through a second control valve 5, and the pressurized hydrogen and nitrogen gas enters a membrane separation device 7 and then enters a pressure swing adsorption separation device 9 through a third control valve 8. The separated high-purity hydrogen (the concentration can reach more than 99.97%) enters a first membrane humidifier 11 after passing through a fourth control valve 10, and the separated desorbed gas returns to the membrane separation device 7 through the fourth control valve 10; the separated high-purity hydrogen enters the anode side of the fuel cell 13 together with the hydrogen flowing back from the ejector 12 after the humidity of the separated high-purity hydrogen is adjusted by the first membrane humidifier 11; the air compressor 16 compresses air, adjusts humidity through the second membrane humidifier 15, and then sends the air to the cathode side of the fuel cell 13; after passing through the fuel cell 13, the anode gas of the fuel cell 13 is discharged from a first outlet of the fuel cell 13, and then the tail gas is returned through the ejector 12, and the cathode gas of the fuel cell 13 is discharged from a second outlet of the fuel cell 13, and then the tail gas passes through a first gas-water separator 14, so that pollution-free air and water are discharged; the first gas-water separator 14 pumps the collected liquid water to the water pressure of the first membrane humidifier 11 and the second membrane humidifier 15, respectively, which maintains the one-side membrane; the electric energy output from the fuel cell 13 passes through the DC/DC converter 17, is connected to the battery pack 18 and the capacitor 19, and is connected to the DC load 20, the inverter, and the ac load 21.
As shown in fig. 3, the control method of the fuel cell power generation system includes the steps of:
s101: starting the heating device, when the temperature inside the ammonia decomposition device 1 reaches a preset temperature (the temperature of the upstream part of the ammonia decomposition device 1 reaches 480 ℃ and the temperature of the downstream part reaches 500-650 ℃), sending ammonia gas into the ammonia decomposition device 1, and decomposing the ammonia gas into hydrogen and nitrogen;
s102: the decomposed hydrogen and nitrogen gas enters an ammonia removal device 4 to remove the undecomposed ammonia gas;
s103: the deaminated hydrogen and nitrogen enter a hydrogen booster pump 6, and the pressure of the hydrogen and nitrogen is increased to a preset pressure (0.1MPa-0.4 MPa);
s104: the pressurized hydrogen and nitrogen enter a membrane separation device 7 to carry out primary separation on hydrogen, and the hydrogen and nitrogen after membrane separation enter a pressure swing adsorption separation device 9 to carry out secondary separation on the hydrogen;
s105: the separated hydrogen and nitrogen enter the anode of the fuel cell 13 after being subjected to humidity adjustment by the first membrane humidifier 11, and the compressed air enters the cathode of the fuel cell 13 after being subjected to humidity adjustment by the second membrane humidifier 15; gas generated by the anode of the fuel cell 13 flows back to the ammonia decomposition device 1, the pressure swing adsorption separation device 9 and the anode of the fuel cell 13 under the action of the ejector 12, gas generated by the cathode of the fuel cell 13 is separated into air and water through the first gas-water separator 14, and the first gas-water separator 14 sends the separated water into the first membrane humidifier 11 and the second membrane humidifier 15 respectively;
s106: the conversion means boosts the voltage of the fuel cell 13 and stores the generated electric energy to the battery pack 18.
In addition to the effects set forth above, the fuel cell power generation system of this embodiment has advantageous effects including:
compared with ammonia combustion and ammonia direct oxidation fuel cells (not including SOFC), the fuel cell has high power generation efficiency after ammonia is decomposed to produce hydrogen, and high-grade electric energy is obtained; meanwhile, compared with other ammonia decomposition hydrogen production devices or methods which rely on high temperature (800-; compared with a single ammonia decomposition catalyst filling device with similar reaction temperature, the ammonia decomposition hydrogen production device can also realize ammonia decomposition hydrogen production under higher air pressure and the same decomposition rate by adjusting the relationship between the catalyst proportion and the temperature of the catalyst bed layer.
This embodiment provides the possibility of adjusting the anode gas pressure, humidity and equivalence ratio, suppresses the negative impact of the nitrogen component on the fuel cell performance, and achieves the dual advantages of reducing the pressure swing adsorption equipment investment and fuel cell performance temperature after the membrane separation provides 95% pure hydrogen.
This embodiment utilizes the compressed air of air compressor machine to the hydrogen pressure boost, has realized the temperature control to hydrogen and air pressure difference. Meanwhile, the invention carries out full combustion heat exchange utilization on the hydrogen tail gas, so that the ammonia fuel cell system does not need to additionally consume other fuels, and does not need to use higher proportion of electric energy for heating the ammonia decomposition hydrogen production device.
Example 2
As shown in fig. 2, the present invention also provides another fuel cell power generation system including: the ammonia decomposition device 1, the heating device 2, the ammonia removal device 4, the fuel cell 13, the conversion device, the battery pack 18, the third membrane humidifier 24, the hydrogen circulation pump 23, the booster pump 22, the second gas-water separator 25, and the air compressor 16. The heating device 2 is installed inside the ammonia decomposition device 1, the heating device 2 is used for heating gas and catalyst, and the ammonia decomposition device 1 is used for decomposing ammonia gas into hydrogen and nitrogen.
The ammonia removal device 4 is communicated with the outlet of the ammonia decomposition device 1 and is used for removing undecomposed ammonia gas; the fuel cell 13 is in communication with the ammonia removal device 4 and oxidizes hydrogen as a fuel to generate electrical energy. The converter is connected to the fuel cell 13, and boosts the voltage of the fuel cell 13; the battery pack 18 is used to store electric energy generated by the hydrogen fuel cell 13. The booster pump 22 is communicated between the ammonia decomposition device 1 and the anode of the fuel cell 13; the air compressor 16 is used for sending compressed air into the booster pump 22, and the third membrane humidifier 24 is communicated between the booster pump 22 and the cathode of the fuel cell 13; the first outlet of the fuel cell 13 is communicated with the inlet of the hydrogen circulating pump 23, the first outlet of the hydrogen circulating pump 23 is communicated with the inlet of the ammonia decomposition device 1, the second outlet of the hydrogen circulating pump 23 is communicated with the anode of the fuel cell 13, the second outlet of the fuel cell 13 is communicated with the inlet of a third gas-water separator, and the outlet of the third gas-water separator is communicated with a third membrane humidifier 24. Meanwhile, a hydrogen booster pump 6 and a membrane separation device 7 are further arranged in the system, the hydrogen booster pump 6 and the membrane separation device 7 are sequentially connected between the ammonia removal device 4 and the booster pump 22, and the outlet of the membrane separation device 7 is also communicated with the first outlet of the hydrogen circulating pump 23.
Compared with the first embodiment, in the fuel cell power generation system provided by this embodiment, the tail gas generated by the anode of the fuel cell 13 is sent to the anode of the fuel cell 13 by the hydrogen circulating pump 23, and the anode exhaust gas of the fuel cell 13 is used for humidification, so that the purity of the anode hydrogen can be ensured, but the humidification of the anode exhaust gas of the fuel cell 13 is insufficient. Aiming at the problem of insufficient humidification of the hydrogen at the anode of the fuel cell 13, the hydrogen is pressurized to 0.2-0.3MPa by a booster pump 22 before entering the fuel cell 13, namely the anode of the fuel cell 13; the cathode of the fuel cell 13, namely the pressure reduction side, is connected with the air compressor 16, the outlet of the pressure increasing side of the booster pump 22 is connected with a pipeline returned by the hydrogen circulating pump 23, the hydrogen circulating pump 23 is used for recovering moisture according to the control of specific working conditions, and the humidity is controlled to be 10-90% RH; the third membrane humidifier 24 realizes the humidity exchange between the cathode tail gas of the fuel cell 13 and the gas at the outlet of the air compressor 16 of the fuel cell 13. The concentration of the hydrogen gas at the anode of the fuel cell 13 in the first example is 99.97% or more, and the concentration of the hydrogen gas at the anode of the fuel cell 13 in the second example is 90-95% pure. With the second embodiment, when the proton membrane of the stack of the fuel cell 13 is thick, the problem of membrane dry-out easily occurs on the anode side of the fuel cell 13.
Wherein, the anode side of the fuel cell 13 is provided with a hydrogen circulating pump 23, and the pressure entering the electric pile of the fuel cell 13 is controlled between 0.2MPa and 0.3 MPa. The air compressor 16 supplies air in an excess ratio of 1.6 to 1.8, and the pressure is reduced to 0.12 to 0.22MPa after passing through the decompression side of the booster pump 22. The second gas-water separator 25 separates gas and water on the cathode side of the fuel cell 13, thereby realizing control of cathode inlet air humidity.
The working process of the fuel cell power generation system is as follows:
ammonia enters the ammonia decomposition device 1 after passing through a flowmeter, is supplied with heat by an electric heater and a tail gas combustion device, and is heated with a catalyst to be decomposed into hydrogen and nitrogen; specifically, the two modes supply heat together when the catalyst is started, the electric heating system only plays a role in controlling the temperature after the catalyst is started, so that ammonia is decomposed into hydrogen and nitrogen in a catalyst bed, the decomposition rate reaches over 99.8%, the decomposition pressure can be increased to 0.5MPa according to the rear end requirement, and the catalyst is realized by cooperating with a rear-end electric heater and a bed with high Ni-based catalyst content. The decomposed hydrogen and nitrogen gas passes through a first control valve 3 and then enters an ammonia removal device 4, and undecomposed ammonia gas is removed to obtain the hydrogen and nitrogen gas with the ammonia content of less than 0.1 ppm; the deaminated hydrogen and nitrogen gas passes through a second control valve 5 and then enters a hydrogen booster pump 6, the pressurized hydrogen and nitrogen gas enters a membrane separation device 7, the obtained hydrogen with the purity of 90-95 percent directly enters a booster pump 22, the hydrogen is pressurized according to 1-4 times of the pressure reduction value at the other side, and the gas which does not penetrate through the membrane of the membrane separation device 7 returns to an electric heater and a combustion device for combustion and heat supply; after the pressure of the hydrogen is regulated by the booster pump 22, the hydrogen and the hydrogen reflowing from the hydrogen circulating pump 23 enter the anode side of the fuel cell 13 together, the hydrogen circulating pump 23 controls the returned humidity and the equivalence ratio of the hydrogen entering the galvanic pile according to instructions, and the discharged hydrogen is intermittently introduced into the electric heater and the combustion device from a bypass to be combusted and supplied heat; the cathode side gas supply of the fuel cell 13 is obtained by pumping through a third membrane humidifier 24 from an air compressor 16; the anode gas flows back through the hydrogen circulating pump 23 after passing through the fuel cell 13, and the cathode gas discharges pollution-free air and water after passing through the second gas-water separator 25; the second gas-water separator 25 separates gas and water to ensure the humidity control of the air entering the pile; the electric energy output from the fuel cell 13 passes through the DC/DC converter 17, is connected to the lithium battery pack 18 and the capacitor 19, and is connected to the DC load 20, the inverter, and the ac load 21.
As shown in fig. 4, the control method of the fuel cell power generation system includes the steps of:
s201: starting the heating device, when the temperature inside the ammonia decomposition device 1 reaches a preset temperature (the temperature of the upstream part of the ammonia decomposition device 1 reaches 480 ℃ and the temperature of the downstream part reaches 500-650 ℃), sending ammonia gas into the ammonia decomposition device 1, and decomposing the ammonia gas into hydrogen and nitrogen;
s202: the decomposed hydrogen and nitrogen gas enters an ammonia removal device 4 to remove the undecomposed ammonia gas;
s203: the deaminated hydrogen and nitrogen enter a hydrogen booster pump 6, and the pressure of the hydrogen and nitrogen is increased to a preset pressure (0.1MPa-0.4 MPa);
s204: the pressurized hydrogen and nitrogen enter a membrane separation device 7 to carry out membrane separation on the hydrogen, and the hydrogen and nitrogen after membrane separation are pressurized by a booster pump 22 and then are sent to the anode of the fuel cell 13; the compressed air is pressurized by a booster pump 22 and then sent to a third membrane humidifier 24, and the compressed air enters the cathode of the fuel cell 13 after being subjected to humidity adjustment by the third membrane humidifier 24; the gas generated at the anode of the fuel cell 13 returns to the ammonia decomposition device 1, the membrane separation device 7 and the anode of the fuel cell 13 under the action of the hydrogen circulating pump 23, the gas generated at the cathode of the fuel cell 13 is separated into air and water by the second gas-water separator 25, and the second gas-water separator 25 sends the separated water to the third membrane humidifier 24;
s205: the conversion means boosts the voltage of the fuel cell 13 and stores the generated electric energy to the battery pack 18.
This embodiment has hydrogen energy storage density height, energy conversion efficiency is high, investment cost is low, the advantage of low power generation cost, because do not need pressure swing adsorption separator, the initial investment and the volume of system all can reduce by a wide margin, utilize the hydrogen of 90-95% purity that membrane separation provided, combine the temperature of hydrogen booster pump and circulating pump, humidity, pressure, equivalence ratio coupling control, the performance negative effects that nitrogen gas accumulation leads to in the current fuel cell system has effectively been solved, and the energy recovery that utilizes the air compressor machine is as hydrogen side pressure boost, also effectively solved in the ammonia decomposition hydrogen manufacturing system, the difficult problem of hydrogen and nitrogen not enough pressure, if in the embodiment that does not have membrane separator, this design method will play more important effect. The embodiment has the advantages of season-crossing, long-term-efficiency energy storage, high power generation efficiency, low electricity consumption cost, low initial investment, low operation and maintenance pressure, no pollutant discharge and the like in application scenes such as a base station power supply, a generator set, peak shaving of a power station, a mine truck, an electric ship and the like.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (11)
1. A fuel cell power generation system comprising:
the ammonia decomposition device is used for decomposing ammonia gas into hydrogen and nitrogen;
the ammonia removal device is communicated with the outlet of the ammonia decomposition device and is used for removing undecomposed ammonia gas;
a fuel cell, which is communicated with the ammonia removal device and takes hydrogen as fuel to be oxidized to generate electric energy;
a converter connected to the fuel cell and boosting a voltage of the fuel cell;
a battery pack for storing electric energy generated by the fuel cell;
the system is characterized by also comprising a first membrane humidifier, a second membrane humidifier, a first gas-water separator and an air compressor; the first membrane humidifier is communicated between the ammonia decomposition device and the anode of the fuel cell, the second membrane humidifier is communicated between the air compressor and the cathode of the fuel cell, and the air compressor is used for sending compressed air to the cathode of the fuel cell; the first outlet of the fuel cell is communicated with the anode of the fuel cell, the second outlet of the fuel cell is communicated with the inlet of the first gas-water separator, the first outlet of the first gas-water separator is communicated with the first membrane humidifier, and the second outlet of the first gas-water separator is communicated with the second membrane humidifier.
2. The fuel cell power generation system according to claim 1, further comprising a membrane separation device and a pressure swing adsorption separation device, wherein an inlet of the pressure swing adsorption separation device is communicated with an outlet of the membrane separation device, an outlet of the ammonia removal device is communicated with an inlet of the membrane separation device, and an outlet of the pressure swing adsorption separation device is communicated with the anode of the fuel cell through the first membrane humidifier.
3. A fuel cell power generation system according to claim 2, further comprising a hydrogen booster pump connected between the ammonia removal device outlet and the inlet of the membrane separation device.
4. The fuel cell power generation system of claim 3, further comprising an ejector, wherein an inlet of the ejector is communicated with the first outlet of the fuel cell, the first outlet of the ejector is respectively communicated with an outlet of the pressure swing adsorption separation device and an inlet of the ammonia decomposition device, and the second outlet of the ejector is communicated with the anode of the fuel cell.
5. The fuel cell power generation system according to claim 4, wherein the heating device comprises an electric heater and a tail gas combustion device, the ammonia decomposition device is internally isolated by two first and second decomposition spaces which can conduct heat, the tail gas combustion device is installed in the first decomposition space, and the electric heater is installed in the second decomposition space; the first decomposition space is communicated with a first inlet of the ammonia decomposition device and a first outlet of the ejector respectively, the second decomposition space is communicated with a second inlet of the ammonia decomposition device, ammonia gas enters the second decomposition space, and the first decomposition space and the second decomposition space are communicated with an outlet of the ammonia decomposition device.
6. The power generation system according to claim 5, wherein two kinds of catalysts are packed in the second decomposition space in the flow direction of the ammonia gas, and the proportion of the first catalyst disposed near the upstream side of the ammonia gas is gradually increased, and the proportion of the second catalyst disposed near the downstream side of the ammonia gas is gradually increased.
7. The fuel cell power generation system according to claim 6, wherein the first catalyst is a Ru-based catalyst, the second catalyst is a Ni-based catalyst, and each of the catalyst paths is packed in a gradient manner and has a catalyst particle diameter of 0.5mm to 3 mm.
8. A fuel cell power generation system comprising:
the ammonia decomposition device is used for decomposing ammonia gas into hydrogen and nitrogen;
the ammonia removal device is communicated with the outlet of the ammonia decomposition device and is used for removing undecomposed ammonia gas;
a fuel cell, which is communicated with the ammonia removal device and takes hydrogen as fuel to be oxidized to generate electric energy;
a converter connected to the fuel cell and boosting a voltage of the fuel cell;
a battery pack for storing electric energy generated by the hydrogen fuel cell;
the system is characterized by further comprising a booster pump, a hydrogen circulating pump, a third membrane humidifier, a second gas-water separator and an air compressor, wherein the inlet of the booster pump is connected with the outlet of the ammonia removal device, the outlet of the booster pump is communicated with the anode of the fuel cell, and the air compressor is used for sending compressed air into the booster pump;
the third membrane humidifier is communicated between the booster pump and the cathode of the fuel cell; the first outlet of the fuel cell is communicated with the inlet of the hydrogen circulating pump, the first outlet of the hydrogen circulating pump is communicated with the inlet of the ammonia decomposition device, the second outlet of the hydrogen circulating pump is communicated with the anode of the fuel cell, the second outlet of the fuel cell is communicated with the inlet of the second gas-water separator, and the outlet of the second gas-water separator is communicated with the third membrane humidifier.
9. The fuel cell power generation system according to claim 8, further comprising a hydrogen booster pump and a membrane separation device, a first outlet of the membrane separation device being in communication with a first outlet of the hydrogen circulation pump, a second outlet of the membrane separation device being in communication with the booster pump, an inlet of the hydrogen booster pump being in communication with the ammonia removal device outlet, an outlet of the hydrogen booster pump being in communication with the membrane separation device inlet.
10. A control method of a fuel cell power generation system, characterized in that the method is applied to the fuel cell power generation system according to claim 6, comprising the steps of:
s101: starting the heating device, and when the interior of the ammonia decomposition device reaches a preset temperature, sending ammonia gas into the ammonia decomposition device to decompose the ammonia gas into hydrogen and nitrogen;
s102: the decomposed hydrogen and nitrogen gas enters an ammonia removal device to remove undecomposed ammonia gas;
s103: the deaminated hydrogen and nitrogen enter a hydrogen booster pump, and the hydrogen and nitrogen are boosted to a preset pressure;
s104: the pressurized hydrogen and nitrogen enter a membrane separation device to carry out primary separation on hydrogen, and the hydrogen and nitrogen after membrane separation enter a pressure swing adsorption separation device to carry out secondary separation on the hydrogen;
s105: the separated hydrogen and nitrogen enter the anode of the fuel cell after the humidity of the hydrogen and nitrogen is adjusted by the first membrane humidifier, and the compressed air enters the cathode of the fuel cell after the humidity of the compressed air is adjusted by the second membrane humidifier; gas generated by the anode of the fuel cell flows back to the ammonia decomposition device, the pressure swing adsorption separation device and the anode of the fuel cell under the action of the ejector, the gas generated by the cathode of the fuel cell is separated into air and water through the first gas-water separator, and the first gas-water separator respectively sends the separated water to the first membrane humidifier and the second membrane humidifier;
s106: the conversion means boosts the fuel cell voltage and stores the generated electric energy to the battery pack.
11. A control method of a fuel cell power generation system, characterized in that the method is applied to the fuel cell power generation system according to claim 9, comprising the steps of:
s201: starting the heating device, and when the interior of the ammonia decomposition device reaches a preset temperature, sending ammonia gas into the ammonia decomposition device to decompose the ammonia gas into hydrogen and nitrogen;
s202: the decomposed hydrogen and nitrogen gas enters an ammonia removal device to remove undecomposed ammonia gas;
s203: the deaminated hydrogen and nitrogen enter a hydrogen booster pump, and the hydrogen and nitrogen are boosted to a preset pressure;
s204: the pressurized hydrogen and nitrogen enter a membrane separation device to carry out membrane separation on the hydrogen, and the hydrogen and nitrogen after membrane separation are pressurized by a booster pump and then are sent to the anode of the fuel cell; the compressed air is pressurized by a booster pump and then sent into a third membrane humidifier, and the compressed air enters the cathode of the fuel cell after the humidity of the compressed air is adjusted by the third membrane humidifier; gas generated by the anode of the fuel cell flows back to the ammonia decomposition device, the membrane separation device and the anode of the fuel cell under the action of a hydrogen circulating pump, the gas generated by the cathode of the fuel cell is separated into air and water through a second gas-water separator, and the second gas-water separator sends the separated water to a third membrane humidifier;
s205: the conversion means boosts the fuel cell voltage and stores the generated electric energy to the battery pack.
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| CN202210705379.0A CN115036539B (en) | 2022-06-21 | 2022-06-21 | Fuel cell power generation system and control method thereof |
| PCT/CN2023/100917 WO2023246669A1 (en) | 2022-06-21 | 2023-06-18 | Fuel cell power generation system and control method therefor |
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| CN202210705379.0A CN115036539B (en) | 2022-06-21 | 2022-06-21 | Fuel cell power generation system and control method thereof |
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| WO2023246669A1 (en) | 2023-12-28 |
| CN115036539B (en) | 2024-01-23 |
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